Insoluble azo dyes



F'atented Dec. 9, 1941 Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application January 29, 1941, Se- I rial No. 376,470. In Great Britain September 14 Claims. 01. 260-156) This invention relates to new insoluble dyestuffs, to superior dyeings produced from said dyestuffs and to methods of producing the same.

According to the invention We cause to interact aminoarylpyridines with o-hydroxyaryl carboxylic acids, or with reactive derivatives of such acids, in such a way that arylamides of the said o-hydroxyaryl carboxylic acids are produced, capable of coupling with diazonium compounds in a position ortho to the hydroxy group.

Suitable o-hydroxyaryl carboxylic acids for use in the above manner include 2:3-hydroxynaphthoic acid, 6-bromoand 6-methoxy-2:3- hydroxynaphthoic acids, 2:3-hydroxycarbazole carboxylic acid, 2:3-hydroxy diphenylene oxide carboxylic acid, and 2:3-hydroxyanthracene carboxylic acid.

The new arylamides are coupled with diazonium compounds on cellulose fibers, such as cotton, regenerated cellulose and similar dyeable fibers, thereby dyeing the fiber. The arylamides are convenient to dissolve and possess unusually high affinity for cellulosic fiber when applied thereto from .aqueous caustic alkali solution.

The azoic colors produced on such fibers as the 7 result of coupling on the fiber with diazonium compounds have good rubbing fastness and excellent general fastness properties. If desired, the diazonium compounds may be applied in the form of stable derivatives to develop the insoluble azo dyestuffs on the fiber.

The diazonium compounds employed may be derived from aromatic amines commonly used for making azoic colors such as, for example, or m-chloroaniline, 4-chloro-2-aminoanisole and 4-nitro-2-aminoanisole.

The invention is illustrated but not limited by the following examples in which the parts are by Weight.

Example I 3 parts of N-(2'-hydroxy-3'-naphthoyl) 4- alpha-pyridyl-aniline which contains some of the corresponding beta and gamma compound are made into a paste with 10 parts of Turkey red oil neutralized with caustic soda and containing 50% of Water, and 60 parts of boiling water are added, followed by 6 parts of aqueous sodium hydroxide liquor of sp. gr. 1.30. The solution is made up to 1,000 parts by adding 921 parts of cold water containing 10 parts of sodium chloride. 50 parts of cotton yarn are soaked for 20 minutes in this solution, squeezed well and immersed in 1,000 parts of a solution containing 2 parts of diazotized -nitro-2-amino-anisole.

The cotton is turned for 20 minutes, squeezed, rinsed with cold water and then boiled in a solution containing 2 parts of sodium carbonate and 3 parts of soap per 1,000 parts. A bluish-red shade is obtained having good fastness to chlorine, kier boiling, boiling sodium carbonate soldtion and light. The following table afiords a list of further combinations together with the shades produced which are obtained by replacing the diazotized 5-nitro-2-amino-anisole in the above example by other diazonium compounds.

- Shade pro- Dlazonlum compound of duced o-Chloraniline i carlet. m-Chloranilinc Scarlet. 4-chloro-2-amino-anisola Bluish-red 5-chloro-2-aminctoluene. ed. 2:5-dichloraniline Scarlet. 4-bcnzoylamino-2:fi-diethox Blue. 4-nitro-2-amino-anisole. Red. l-amino-anthraquinone Red. 3-nitro-4-amino-toluene Red. 4-chloro-2-nitroaniline Red.

The coupling component used in this example maybe made as follows: 10 parts of l-aminoalpha-phenylpyridine mixed with the corresponding beta and gamma compounds, the mixture being made as described below, are dissolved in 175 parts of toluene, 11.0 parts of 2:3-hydroxynaphthoic acid are added and the solution, is stirred and heated to boiling under a reflux condenser. 3.0 parts of phosphorus trichloride are added during 1 hour. The mixture is boiled for a further 15 hours, cooled and poured into parts of 10% aqueous solution of sodium carbonate. The toluene is driven off by distillation in steam. The substance remaining undissolved in the aqueous sodium carbonate is then filtered off and dissolved in a suificiency of aqueous sodium hydroxide solution. After filtration of the solution when necessary, the new compound is precipitated by the addition of acid, filtered off, washed with water and dried. The product is N '2'- hydroxy 3'- naphthoyl) -4-alpha-pyridyl-aniline mixed with the corresponding beta and gamma compounds, and has a high afiimty for cellulosic fiber.

The mixture of 4-amino-alpha-phenylpyridine and the corresponding beta and gamma compounds used above is made by reacting pyridine with diazotized l-amino-l-nitrobenzene according to the method described in Britishapplication No. 26,064/38 and reducing the mixture of isomeric 4-nitrophenylpyridines so obtained.

,. droxy-Bf -naphthoyl) Example II A dyebath was made in the manner described in Example I by using an equivalent amount of N- (2'-vhydroxy-3 carbazole carbonyl) 4 pyridyl-aniline instead of 3 parts of N-(2-hydroxy- 3'-naphthoyl) -4-alpha-pyridyl-aniline. Cotton yarn was dyed in the bath and developed with 5-nitro-2-amino-anisole in the manner described fastness properties was obtained.

Development of the direct dyeing made with N- (2'-hydroxy-3-carbazole-carbonyl) -4=pyridylaniline with 4-nitro-2-amino toluene gave" a brown shade. amino-anisole gave a brown shade and development with 4-benzoylamino-2,5-diethoxy-aniline Development with -4 ch1oro-2- gave a dark reddish blue shade. Allof these dyeings had excellent fastness properties similar" to those of the dyeing described in Example I.

. By using N-(2'-hydroxy-3'-carbazole-car- 'bonyl) -4-picolyl-aniline instead of the corresponding pyridyl aniline, a dyeing having abrown shade and excellent fastness properties was pro- 'duced. Instead of using the plcolyl aniline, the

"aryl-substituted methyl-, methoxy-, nitroor 'chloro-picolyl derivatives can be used. These anilides give dyeings having excellent fastness properties in modified shades.

' Example III By making the direct dyeing with N-(2'-'hyr-4-pyridy1-2-methylaniline and. similarly developing, dyeings having excellent fastness properties were produced on cotton fiber as follows:

Diazonium compound of- Shade produced fi-nitro-2-amino-anisole Red. Red.

4-nitro-2-amino-toluene fi-chloro-Z-amino-toluene 3-nitro4-amino-toluene l-amino-anthraquinone Example IV By dyeing cotton fibers with N- (z hydroxy- V 3 -na'phthoyl) -4-picolyl-aniline in accordance with the procedure of ExampleI instead of the pyridyl aniline described therein and then developing with 5-nitro-2-amino-anisole, the fibers were "dyed a red shade having'other properties similarto those of the dyeings of Example I;

Example V above examples are mentioned the derivatives "of "N- (2'-hydroxy-3 -diphenylene-oxide carbonyl) 4-pyridyl-aniline which ares ubstituted in the benzene nucleus of the phenyl pyridine group by methyl,'methoxy, nitro or chloro; theanilides derived from 2 hydroxy-3-diphenylene-oxidecarboxylic acid and 4-picolyl-aniline or the derivatives thereof which are substituted in the benzene nucleus by methyl, methoxy, nitro or chloro; theanilides derived irom ti brcmo vor 6-methoxy-2,3-hydroxy-naphthoic acid and 4-pyridylor 4-picolyl-anilines; the anilides derived from 2,3-hydroxy-anthracene-carboxylic in Example I A brown Shade having eXceueh-fi I 3 is devoid of solubilizing groups, such as those used for'making azoic colors.

' This is' a continuation-in-part of our application Serial No. 295,912, filed September 21, 1939.

From the foregoing disclosure it will be recognized thatthe'invention is susceptible of modification without departing from the spirit and scope thereof and it is to be understood that the invention is not restricted to the specific illustrations thereof herein set forth.

We claim:

1. Compounds having the formula in which A represents one of a grouprconsisting of the radicals of l-amino-anthraquinone and the primary arylamines 'Of the benzene series which are devoid of solubilizing groups; and B is the radical of a coupling component represented by the formula in which the hydroxy and the group CONHR- are in ortho positions to each other and wherein Z is one of a group consisting of the radicals of naphthalene, the 6-br0mo and 6-methoxy derivatives thereof, carbazole, diphenylene oxide andanthracene; and R is from the group consisting of the radicals of C-phenyl pyridine,

C-phenyl picoline and the methyl, methoxy,

primary arylamines of the benzene series which are devoid of solubilizin'g groups coupled to the radical of a pyridyl-ortho toluidideof z-hydroxy-3-naphth'oic acid. 7 M

4. An azo compound having as diazo component one of a group consisting of the radical of l-amino-anthraquinohe and the radicals of primary arylamines of thebenzene series which are devoidof solubilizingf groups coupled to [the radical of a pyridyl anilide of 2-hydroxy-carbazole-3-carboxylic acid. l

5. The compoundrepresentedby the formula 6. The compound represented by the formula, 8. Cellulosic fibers dyed with the compound N of claim 1.

9. C'ellulosic fibers dyed with the compound 1 T of claim 2.

H30 N=N OH! i L 5 10. Ce11u1os1c fibers dyed wlth the compound of clalm 3.

NO 11. C-ellulosic fibers dyed with the compound 2 H of claim 4.

12. Cellulosic fibers dyed with the compound 7. The compound represented by the formula, 10 of claim 5.

13. Cellulosic fibers dyed with the compound mm (|)H IITOHNOC 0-H of claim 6.'

l l 14. Cellulosic fibers dyed with the compound OZNC N=N- H- H of claim 7.

K 15 ARNOLD KERSHAW.

HN\ l KENNETH HERBERT SAUNDERS. 

